U.S. patent number 5,399,275 [Application Number 08/166,125] was granted by the patent office on 1995-03-21 for environmentally friendly viscosity index improving compositions.
This patent grant is currently assigned to The Lubrizol Corporation. Invention is credited to Richard M. Lange, Conrad A. Mamajek, Joseph G. Seebauer.
United States Patent |
5,399,275 |
Lange , et al. |
March 21, 1995 |
Environmentally friendly viscosity index improving compositions
Abstract
A lubricant composition having improved viscosity index
characteristics is described that comprises (A) at least one
vegetable or synthetic triglyceride oil of the formula ##STR1##
wherein R.sup.1, R.sup.2 and R.sup.3 are aliphatic hydrocarbyl
groups having at least 60 percent monounsaturated character and
containing from about 6 to about 24 carbon atoms and further
wherein an oleic acid moiety:linoleic acid moiety is from about 2
up to about 90 and (B) at least one mixed ester of a
carboxy-containing interpolymer. Optionally, the composition may
also contain (C) a synthetic ester base oil, and (D) an
antioxidant.
Inventors: |
Lange; Richard M. (Euclid,
OH), Seebauer; Joseph G. (Mentor-on-the-Lake, OH),
Mamajek; Conrad A. (Hudson, OH) |
Assignee: |
The Lubrizol Corporation
(Wickliffe, OH)
|
Family
ID: |
25539148 |
Appl.
No.: |
08/166,125 |
Filed: |
December 10, 1993 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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993143 |
Dec 18, 1992 |
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Current U.S.
Class: |
508/470; 508/235;
508/442 |
Current CPC
Class: |
C10M
169/044 (20130101); C10M 129/14 (20130101); C10M
135/30 (20130101); C10M 145/10 (20130101); C10M
145/38 (20130101); C10M 101/04 (20130101); C10M
105/38 (20130101); C10M 149/02 (20130101); C10M
137/02 (20130101); C10M 129/10 (20130101); C10M
133/12 (20130101); C10M 107/34 (20130101); C10M
169/044 (20130101); C10M 101/04 (20130101); C10M
105/38 (20130101); C10M 107/34 (20130101); C10M
129/10 (20130101); C10M 129/14 (20130101); C10M
133/12 (20130101); C10M 135/30 (20130101); C10M
137/02 (20130101); C10M 145/10 (20130101); C10M
145/38 (20130101); C10M 149/02 (20130101); C10M
2209/082 (20130101); C10M 2209/105 (20130101); C10M
2223/04 (20130101); C10N 2040/255 (20200501); C10M
2207/026 (20130101); C10M 2219/087 (20130101); C10M
2215/06 (20130101); C10N 2040/00 (20130101); C10M
2217/02 (20130101); C10N 2040/08 (20130101); C10N
2040/252 (20200501); C10M 2207/2835 (20130101); C10N
2040/38 (20200501); C10N 2040/06 (20130101); C10M
2209/1085 (20130101); C10M 2215/067 (20130101); C10M
2207/404 (20130101); C10M 2209/08 (20130101); C10N
2040/30 (20130101); C10N 2040/32 (20130101); C10M
2223/10 (20130101); C10N 2040/36 (20130101); C10M
2217/06 (20130101); C10M 2209/106 (20130101); C10M
2209/1095 (20130101); C10M 2217/046 (20130101); C10M
2223/049 (20130101); C10N 2040/25 (20130101); C10M
2207/023 (20130101); C10M 2209/1045 (20130101); C10M
2209/104 (20130101); C10N 2040/50 (20200501); C10N
2040/253 (20200501); C10M 2217/024 (20130101); C10M
2207/401 (20130101); C10M 2209/1055 (20130101); C10M
2207/027 (20130101); C10M 2215/064 (20130101); C10M
2223/042 (20130101); C10M 2207/40 (20130101); C10M
2215/066 (20130101); C10N 2040/42 (20200501); C10M
2207/024 (20130101); C10M 2209/1065 (20130101); C10M
2219/088 (20130101); C10M 2215/04 (20130101); C10M
2215/068 (20130101); C10M 2219/089 (20130101); C10M
2209/109 (20130101); C10M 2223/02 (20130101); C10M
2207/4045 (20130101); C10M 2215/26 (20130101); C10N
2040/28 (20130101); C10N 2040/34 (20130101); C10N
2040/40 (20200501); C10M 2209/1033 (20130101); C10M
2209/086 (20130101); C10M 2209/1075 (20130101); C10M
2217/028 (20130101); C10M 2215/065 (20130101); C10N
2040/251 (20200501); C10N 2040/44 (20200501) |
Current International
Class: |
C10M
169/04 (20060101); C10M 169/00 (20060101); C10M
141/000 () |
Field of
Search: |
;252/51.5A,56S,56R,50,49.8 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Howard; Jacqueline V.
Attorney, Agent or Firm: Cordek; James L. Hunter, Sr.;
Frederick D. Fischer; Joseph P.
Parent Case Text
This is a continuation-in-part of copending application Ser. No.
07/993,143 filed on Dec. 18, 1992, now abandoned.
Claims
What is claimed is:
1. An environmentally friendly viscosity index improving
composition comprising:
(A) at least one vegetable or synthetic triglyceride oil of the
formula ##STR14## wherein R.sup.1, R.sup.2 and R.sup.3 are
aliphatic hydrocarbyl groups having at least 60 percent
monounsaturated character and containing from about 6 to about 24
carbon atoms and further wherein an oleic acid moiety:linoleic acid
moiety is from about 2 up to about 90, and
(B) at least one mixed ester of a carboxy-containing
interpolymer.
2. The composition of claim 1 wherein the triglyceride is a
vegetable oil triglyceride comprising high oleic safflower oil,
high oleic corn oil, high oleic rapeseed oil, high oleic sunflower
oil, high oleic soybean oil, high oleic cottonseed oil, high oleic
lesquerella oil, high oleic meadowfoam oil and high oleic palm
olein.
3. The composition of claim 2 wherein the vegetable oil
triglyceride is an ester of at least one straight chain fatty acid
and glycerol wherein the fatty acid contains from about 8 to about
22 carbon atoms.
4. The composition of claim 3 wherein the triglyceride is at least
70 percent monounsaturated.
5. The composition of claim 4 wherein the triglyceride is at least
80 percent monounsaturated.
6. The composition of claim 5 wherein the monounsaturated fatty
acid is oleic acid.
7. The composition of claim 1 wherein the carboxy-containing
interpolymer (B) comprises
(1) a nitrogen-containing mixed ester having an inherent viscosity
of from about 0.05 to about 2 and being derived from at least two
monomers, one of said monomers being a low molecular weight
aliphatic olefin or styrene and the other of said monomers being an
alpha, beta-unsaturated aliphatic acid, dicarboxylic acid,
anhydride or ester thereof, wherein the carboxylic acid,
dicarboxylic acid, anhydride or ester is at least 80 percent
esterified after polymerization and being characterized by the
presence within its polymeric structure of at least one of each of
three pendant polar groups which are derived from the carboxy
groups of said nitrogen-containing ester:
(A) a relatively high molecular weight carboxylic ester group, said
carboxylic ester group having at least 8 aliphatic carbon atoms in
the ester radical,
(B) a relatively low molecular weight carboxylic ester group having
no more than 7 aliphatic carbon atoms in the ester radical,
(C) a carbonyl-polyamino group derived from a polyamino compound
having one primary or secondary amino group, wherein the molar
ratio of (A):(B):(C) is (50-95):(5-50):(0.1-15);
(2) a mixed ester of a terpolymer having an inherent viscosity of
from about 0.05 to about 2, of a low molecular weight aliphatic
olefin or styrene, an alpha, beta-unsaturated carboxylic acid,
dicarboxylic acid, anhydride or ester thereof, and an
interpolymerizable comonomer wherein the carboxylic acid,
dicarboxylic acid, dicarboxylic acid, anhydride or ester is at
least 80 percent esterified and wherein the ester contains pendant
polar groups (A) and (B) wherein:
(A) is a carboxylic ester group having at least 8 aliphatic carbon
atoms in an alkyl portion of the ester radical,
(B) is a relatively low molecular weight carboxylic ester group
having no more than 7 aliphatic carbon atoms in the ester radical,
wherein the molar ratio of (A):(B) is (1-20):(1), and
optionally
(C) a carbonyl-polyamino group derived from a polyamino compound
having one primary or secondary amino group, wherein the molar
ratio of (A):(B):(C) is (50-95):(5-50):(0.1-15); and
(3) a nitrogen-free mixed ester of a carboxy-containing
interpolymer having an inherent viscosity of from about 0.05 to
about 2.0 and being derived from at least two monomers, one of said
monomers being a low molecular weight aliphatic olefin or styrene
and the other of said monomers being an alpha, beta-unsaturated
aliphatic acid, dicarboxylic acid, anhydride or ester thereof,
wherein the carboxylic acid, dicarboxylic acid, anhydride or ester
is at least 80 percent esterified and wherein the ester contains
pendant polar groups (A) and (B) comprising:
(A) a relatively high molecular weight carboxylic ester group, said
carboxylic ester group having at least 8 aliphatic carbon atoms in
the ester radical,
(B) a relatively low molecular weight carboxylic ester group having
no more than 7 aliphatic carbon atoms in the ester radical, wherein
the molar ratio of (A):(B) is (1-20):(1).
8. The composition of claim 7 wherein the alpha, beta-unsaturated
aliphatic acid comprises maleic acid, iraconic acid, acrylic acid
or methacrylic acid.
9. The composition of claim 7 wherein the alpha, beta-unsaturated
aliphatic anhydride comprises maleic anhydride or itaconic
anhydride.
10. The composition of claim 7 wherein the alpha, beta-unsaturated
ester is an acrylic acid ester or methacrylic acid ester.
11. The composition of claim 7 wherein the molar ratio of (A):(B)
is (1-20):(1).
12. The composition of claim 7 wherein the molar ratio of
(A):(B):(C) is (60-80):(15-25):(0.1-10).
13. The composition of claim 7 wherein the ester is at least 90
percent esterified.
14. The composition of claim 7 wherein the inter-polymerizable
comonomer comprises acrylic acid, esters of acrylic acid,
methacrylic acid, esters of methacrylic acid, methacrylamide, and
N-substituted methacrylamides, itaconic acid and anhydride,
citraconic acid and anhydride, isobutylene, diisobutylene and
higher oligomers and methylstyrene monomers.
15. The composition of claim 7 wherein the interpolymer is a
styrene-maleic anhydride interpolymer having an inherent viscosity
of from about 0.1 to about 0.8.
16. The composition of claim 7 wherein the relatively high
molecular weight carboxylic ester group of (A) has from 8 to about
24 aliphatic carbon atoms, the relatively low molecular weight
carboxylic ester group of (B) has from 3 to 5 carbon atoms and the
carbonyl-polyamino group of (C) is derived from a
primary-aminoalkyl-substituted tertiary amine.
17. The composition of claim 1 further comprising
(C) a synthetic ester base oil comprising the reaction of a
monocarboxylic acid of the formula
a dicarboxylic acid of the formula ##STR15## or an aryl carboxylic
acid of the formula
wherein R.sup.4 is a hydrocarbyl group containing from about 4 to
about 24 carbon atoms, R.sup.5 is hydrogen or a hydrocarbyl group
containing from about 4 to about 50 carbon atoms, R.sup.6 is
hydrogen or a hydrocarbyl group containing from 1 up to about 24
carbon atoms, m is an integer of from 0 to about 6, and p is an
integer of from 1 to 4; with an alcohol of the formula ##STR16##
wherein R.sup.7 is an aliphatic group containing from 1 to about 24
carbon atoms or an aromatic group containing from 6 to about 18
carbon atoms, R.sup.14 is hydrogen or an alkyl group containing 1
or 2 carbon atoms, t is from 0 to about 40 and n is from 1 to about
6.
18. The composition of claim 17 wherein R.sup.4 contains from about
6 to about 18 carbon atoms.
19. The composition of claim 17 wherein R.sup.5 contains from about
4 to about 24 carbon atoms and m is zero.
20. The composition of claim 17 wherein R.sup.5 is hydrogen and m
is 4.
21. The composition of claim 17 wherein R.sup.6 contains from about
6 to about 18 carbon atoms and p is 2.
22. The composition of claim 17 wherein R.sup.7 contains from about
3 to about 18 carbon atoms.
23. The composition of claim 1 further comprising
(D) an antioxidant selected from the group consisting of
(1) a phenol of Formula I ##STR17## wherein R.sup.8 is hydrogen or
a hydrocarbyl group containing from 1 up to about 24 carbon atoms
and a is an integer of from 1 up to 5, q is an integer of from 1 up
to 3 with the proviso that the sum of a and q does not exceed 6, or
an alkyl phenol of Formula II ##STR18## wherein R.sup.8 is an alkyl
group containing from 1 up to about 24 carbon atoms, X is a sulfur
or methylene, a is an integer of from 1 up to 4, b is an integer of
from 0 up to about 10 and c is an integer of from 1 up to 3;
(2) an aromatic amine of the formula ##STR19## wherein R.sup.9 is
##STR20## and R.sup.10 and R.sup.11 are independently a hydrogen or
an alkyl group containing from 1 up to about 24 carbon atoms and d
is 0 or 1; and
(3) a phosphite ester of the formula ##STR21## wherein each of
R.sup.12 and R.sup.13 is an alkyl group containing from 1 up to
about 24 carbon atoms.
24. The composition of claim 23 wherein within (D)(1) R.sup.8
contains from 1 up to about 8 carbon atoms, q is 1, a is from 1 up
to about 3, c is 1 or 2 and b is from 1 up to about 4.
25. The composition of claim 23 wherein within (D)(2) R.sup.9 is
##STR22## and R.sup.10 and R.sup.11 contain 9 carbon atoms.
26. The composition of claim 23 wherein within (D)(3) R.sup.12 and
R.sup.13 contain from 4 to about 18 carbon atoms.
27. The composition of claim 17 wherein the alcohol is
pentaerythritol, dipentaerythritol, trimethylolpropane, or
bis-trimethylolpropane.
28. The composition of claim 17 further comprising
(D) an antioxidant selected from the group consisting of
(1) a phenol of Formula I ##STR23## wherein R.sup.8 is hydrogen or
a hydrocarbyl group containing from 1 up to about 24 carbon atoms
and a is an integer of from 1 up to 5, q is an integer of from 1 up
to 3 with the proviso that the sum of a and q does not exceed 6, or
an alkyl phenol of Formula II ##STR24## wherein R.sup.8 is an alkyl
group containing from 1 up to about 24 carbon atoms, X is a sulfur
or methylene, a is an integer of from 1 up to 4, b is an integer of
from 0 up to about 10 and c is an integer of from 1 up to 3;
(2) an aromatic amine of the formula ##STR25## wherein R.sup.9 is
##STR26## and R.sup.10 and R.sup.11 are independently a hydrogen or
an alkyl group containing from 1 up to about 24 carbon atoms and d
is 0 or 1; and
(3) a phosphite ester of the formula ##STR27## wherein each of
R.sup.12 and R.sup.13 is a hydrocarbyl group containing from 1 up
to about 24 carbon atoms.
Description
FIELD OF THE INVENTION
The present invention relates to triglyceride oils having viscosity
index improving characteristics wherein the triglyceride oils
contain at least a 60 percent monounsaturated content. Triglyceride
oils containing this viscosity index improver have utility in
passenger car motor oils (PCMO), gear oils, automatic transmissions
fluids (ATF), hydraulic fluids, chain bar lubricants, way
lubricants for machinery operations, diesel lubricants and tractor
fluids.
BACKGROUND OF THE INVENTION
Environmentally friendly fluids comprise mainly vegetable oils.
Vegetable oils have a low viscosity and therefore tend to flow off
surfaces providing poor film forming and thus giving poor
lubrication.
In order to "body up" the vegetable oils a polymeric viscosity
improver is utilized. The problem is in finding a viscosity
improver that is soluble in vegetable oils.
U.S. Pat. No. 4,391,721 (Pappas, Jul. 5, 1983) relates to
dispersant viscosity index improvers that comprise the reaction
product of an aliphatic alcohol or mixtures thereof, a tertiary
amino alcohol and a styrene maleic anhydride copolymer. The
lubricating oil additives of this invention are prepared by first
copolymerizing styrene and maleic anhydride, reacting the copolymer
with a C.sub.6 or greater aliphatic alcohol or mixture of aliphatic
alcohols until the copolymer is substantially completely esterified
and then transesterifying with a tertiary amino alcohol. By
transesterifying, the inventor means displacing the aliphatic
alcohol from a fraction of the ester groups and replacing them in
the ester with a tertiary amino alcohol.
U.S. Pat. Nos. 4,970,011 and 5,094,764 (Kuwamoto et al, Nov. 13,
1990 and Mar. 10, 1992) relate to a lubricating oil composition
containing as essential ingredients a lubricating oil component
having a melting point of not higher than 100.degree. C., and one
or more water-soluble dispersants selected from the group
consisting of anionic polymeric dispersants of a molecular weight
of 250 to 25,000, and polyoxyethylene type surfactants of a
molecular weight of 3,000 to 20,000 and an HLB value of at least
18, said lubricating oil component being present in a stably
dispersed state in water, achieves excellent adhesion when supplied
to a machined portion.
U.S. Pat. No. 3,702,300 (Coleman, Nov. 7, 1972) relates to a
carboxy-containing interpolymer in which some of the carboxy
radicals are esterified and the remaining carboxy radicals are
neutralized by reaction with a polyamino compound having one
primary or secondary amino group which is useful as an additive in
lubricating compositions and fuels. The interpolymer is especially
effective to impart desirable viscosity characteristics and
anti-sludge properties to a lubricating oil.
SUMMARY OF THE INVENTION
An environmentally friendly viscosity index improving composition
is disclosed which comprises
(A) at least one vegetable or synthetic triglyceride oil of the
formula ##STR2## wherein R.sup.1, R.sup.2 and R.sup.3 are aliphatic
hydrocarbyl groups having at least 60 percent monounsaturated
character and containing from about 6 to about 24 carbon atoms,
and
(B) at least one mixed ester of a carboxy-containing
interpolymer.
In addition to components (A) and (B) the composition may also
contain (C) a synthetic ester base oil and/or (D) an
antioxidant.
DETAILED DESCRIPTION OF THE INVENTION
(A) The Triglyceride Oil
In practicing this invention a triglyceride oil is employed which
is a natural or synthetic oil of the formula ##STR3## Within the
triglyceride formula are aliphatic hydrocarbyl groups having at
least 60 percent monounsaturated character and containing from
about 6 to about 24 carbon atoms. The term "hydrocarbyl group" as
used herein denotes a radical having a carbon atom directly
attached to the remainder of the molecule. The aliphatic
hydrocarbyl groups include the following: (1) Aliphatic hydrocarbon
groups; that is, alkyl groups such as heptyl, nonyl, undecyl,
tridecyl, heptadecyl; alkenyl groups containing a single double
bond such as heptenyl, nonenyl, undecenyl, tridecenyl,
heptadecenyl, heneicosenyl; alkenyl groups containing 2 or 3 double
bonds such as 8,11-heptadecadienyl and 8,11,14-heptadecatrienyl.
All isomers of these are included, but straight chain groups are
preferred.
(2) Substituted aliphatic hydrocarbon groups; that is groups
containing non-hydrocarbon substituents which, in the context of
this invention, do not alter the predominantly hydrocarbon
character of the group. Those skilled in the art will be aware of
suitable substituents; examples are hydroxy, carbalkoxy,
(especially lower carbalkoxy) and alkoxy (especially lower alkoxy),
the term, "lower" denoting groups containing not more than 7 carbon
atoms.
(3) Hetero groups; that is, groups which, while having
predominantly aliphatic hydrocarbon character within the context of
this invention, contain atoms other than carbon present in a chain
or ring otherwise composed of aliphatic carbon atoms. Suitable
hetero atoms will be apparent to those skilled in the art and
include, for example, oxygen, nitrogen and sulfur.
Naturally occurring triglycerides are vegetable oil triglycerides.
The synthetic triglycerides are those formed by the reaction of one
mole of glycerol with three moles of a fatty acid or mixture of
fatty acids. Preferred are vegetable oil triglycerides.
Regardless of the source of the triglyceride oil, the fatty acid
moieties are such that the triglyceride has a monounsaturated
character of at least 60 percent, preferably at least 70 percent
and most preferably at least 80 percent. Naturally occurring
triglycerides having utility in this invention are exemplified by
vegetable oils that are genetically modified such that they contain
a higher than normal oleic acid content. Normal sunflower oil has
an oleic acid content of 20-40 percent. By genetically modifying
the seeds of sunflowers, a sunflower oil can be obtained wherein
the oleic content is from about 60 percent up to about 90 percent.
That is, the R.sup.1, R.sup.2 and R.sup.3 groups are heptadecenyl
groups and the R.sup.1 COO.sup.-, R.sup.2 COO.sup.- and R.sup.3
COO.sup.- that are attached to the 1,2,3-propanetriyl group
##STR4## are the residue of an oleic acid molecule. U.S. Pat. Nos.
4,627,192 and 4,743,402 are herein incorporated by reference for
their disclosure to the preparation of high oleic sunflower
oil.
For example, a triglyceride comprised exclusively of an oleic acid
moiety has an oleic acid content of 100% and consequently a
monounsaturated content of 100%. Where the triglyceride is made up
of acid moieties that are 70% oleic acid, 10% stearic acid, 5%
palmitic acid, 7% linoleic and 8% hexadecanoic acid, the
monounsaturated content is 70%. The preferred triglyceride oils are
high oleic (at least 60 percent) acid triglyceride oils. Typical
high oleic vegetable oils employed within the instant invention are
high oleic safflower oil, high oleic corn oil, high oleic rapeseed
oil, high oleic sunflower oil, high oleic soybean oil, high oleic
cottonseed oil, high oleic lesquerella oil, high oleic meadowfoam
oil and high oleic palm olein. A preferred high oleic vegetable oil
is high oleic sunflower oil obtained from Helianthus sp. This
product is available from SVO Enterprises Eastlake, Ohio as
Sunyl.RTM. high oleic sunflower oil. Sunyl 80 is a high oleic
triglyceride wherein the acid moieties comprise 80 percent oleic
acid. Another preferred high oleic vegetable oil is high oleic
rapeseed oil obtained from Brassica campestris or Brassica napus,
also available from SVO Enterprises as RS.RTM. high oleic rapeseed
oil. RS80 signifies a rapeseed oil wherein the acid moieties
comprise 80 percent oleic acid.
It is to be noted the olive oil is excluded as a vegetable oil in
this invention. The oleic acid content of olive oil typically
ranges from 65-85 percent. This content, however, is not achieved
through genetic modification, but rather is naturally
occurring.
It is further to be noted that genetically modified vegetable oils
have high oleic acid contents at the expense of the di-and tri-
unsaturated acids. A normal sunflower oil has from 20-40 percent
oleic acid moieties and from 50-70 percent linoleic acid moieties.
This gives a 90 percent content of mono- and di-unsaturated acid
moieties (20+70 or 40+50). Genetically modifying vegetable oils
generate a low di- or tri-unsaturated moiety vegetable oil. The
genetically modified oils of this invention have an oleic acid
moiety:linoleic acid moiety ratio of from about 2 up to about 90. A
60 percent oleic acid moiety content and 30 percent linoleic acid
moiety content of a triglyceride oil gives a ratio of 2. A
triglyceride oil made up of an 80 percent oleic acid moiety and 10
percent linoleic acid moiety gives a ratio of 8. A triglyceride oil
made up of a 90 percent oleic acid moiety and 1 percent linoleic
acid moiety gives a ratio of 90. The ratio for normal sunflower oil
is 0.5 (30 percent oleic acid moiety and 60 percent linoleic acid
moiety).
Non-genetically modified vegetable oils having utility in this
invention are sunflower oil, safflower oil, corn oil, soybean oil,
rapeseed oil, meadowfoam oil, lesquerella oil or castor oil.
(B) The Carboxy-Containing Interpolymer
The carboxy-containing interpolymer (B) comprises
(1) a nitrogen-containing mixed ester having an inherent viscosity
of from about 0.05 to about 2 and being derived from at least two
monomers, one of said monomers being a low molecular weight
aliphatic olefin or styrene and the other of said monomers being an
alpha, beta-unsaturated aliphatic acid, anhydride or ester thereof,
wherein the carboxylic acid, dicarboxylic acid, anhydride or ester
is at least 80 percent esterified after polymerization and being
characterized by the presence within its polymeric structure of at
least one of each of three pendant polar groups which are derived
from the carboxy groups of said nitrogen-containing ester:
(A) a relatively high molecular weight carboxylic ester group, said
carboxylic ester group having at least 8 aliphatic carbon atoms in
the ester radical,
(B) a relatively low molecular weight carboxylic ester group having
no more than 7 aliphatic carbon atoms in the ester radical,
(C) a carbonyl-polyamino group derived from a polyamino compound
having one primary or secondary amino group, wherein the molar
ratio of (A):(B):(C) is (50-95):(5-50):(0.1-15);
(2) a mixed ester of a terpolymer having an inherent viscosity of
from about 0.05 to about 2, of a vinyl aromatic monomer, an alpha,
beta-unsaturated carboxylic acid, dicarboxylic acid, anhydride or
ester thereof, and an interpolymerizable comonomer wherein the
carboxylic acid, anhydride or ester is at least 80 percent
esterified after polymerization and wherein the ester contains
pendant polar groups (A) and (B) wherein:
(A) is a carboxylic ester group having at least 8 aliphatic carbon
atoms in an alkyl portion of the ester radical,
(B) is a relatively low molecular weight carboxylic ester group
having no more than 7 aliphatic carbon atoms in the ester radical,
wherein the molar ratio of (A):(B) is (1-20):(1), and
optionally
(C) a carbonyl-polyamino group derived from a polyamino compound
having one primary or secondary amino group, wherein the molar
ratio of (A):(B):(C) is (50-95):(5-50):(0.1-15); and
(3) a nitrogen-free mixed ester of a carboxy-containing
interpolymer having an inherent viscosity of from about 0.05 to
about 2.0 and being derived from at least two monomers, one of said
monomers being a low molecular weight aliphatic olefin or styrene
and the other of said monomers being an alpha, beta-unsaturated
aliphatic acid, dicarboxylic acid, anhydride or ester thereof,
wherein the carboxylic acid, anhydride or ester is at least 80
percent esterified after polymerization and wherein the ester
contains pendant polar groups (A) and (B) comprising:
(A) a relatively high molecular weight carboxylic ester group, said
carboxylic ester group having at least 8 aliphatic carbon atoms in
the ester radical,
(B) a relatively low molecular weight carboxylic ester group having
no more than 7 aliphatic carbon atoms in the ester radical, wherein
the molar ratio of (A):(B) is (1-20):(1).
Regardless of which mixed ester of a carboxy-containing
interpolymer is employed, (B)(1), (B)(2) or (B)(3), the
interpolymer has an inherent viscosity of from about 0.05 to about
2. In (B)(1) and (B)(3), the interpolymers are derived from at
least two monomers, one of said monomers being a low molecular
weight aliphatic olefin or styrene and the other of said monomers
being an alpha, beta-unsaturated aliphatic acid anhydride or ester.
In (B)(2) the interpolymer is a terpolymer of the above two
monomers of (B)(1) and (B)(2) and also contains an
interpolymerizable comonomer.
The formed interpolymer is then reacted with alcohols such that the
interpolymer is at least 80 percent esterified. In (B)(1) the ester
is characterized by the presence within its polymeric structure of
pendant polar groups: (A) a relatively high molecular weight
carboxylic ester group having at least 8 aliphatic carbon atoms in
the ester radical, (B) a relatively low molecular weight carboxylic
ester group having no more than 7 aliphatic carbon atoms in the
ester radical, and (C) a carbonyl-polyamino group derived from a
polyamino compound having no primary or secondary amino group,
wherein the molar ratio of (A):(B):(C) is
In (B-2) the mixed ester is a terpolymer wherein the ester is
characterized by the presence within its polymeric structure of
pendant polar groups (A) and (B) as defined above wherein the molar
ratio of (A):(B) is (1-20):(1). Optionally pendant polar group (C)
may be employed and the molar ratio of (A):(B):(C) in (B-2) is the
same as the molar ratio of (A):(B):(C) in (B-1).
In (B-3) the mixed ester is a nitrogen-free mixed ester
characterized by the presence within its polymeric structure of
pendant polar groups (A) and (B) as defined above wherein the molar
ratio (A):(B) in (B-3) is the same as the molar ratio of (A):(B) in
(B-2).
An essential element of the esters of component (B) is that they
are mixed esters, i.e., one in which there is the combined presence
of both a high molecular weight ester group and a low molecular
weight ester group, particularly in the ratios as stated above.
Such combined presence is critical to the viscosity properties of
the mixed ester, both from the standpoint of its viscosity
modifying characteristics and from the standpoint of its thickening
effect upon lubricating compositions in which it is used as an
additive.
In reference to the size of the ester groups, it is pointed out
that an ester radical is represented by the formula
and that the number of carbon atoms in an ester radical is the
combined total of the carbon atoms of the carbonyl group and the
carbon atoms of the ester alkyl group i.e., the (OR) group.
An essential element of Component (B)(1) and optionally of (B)-(2)
is the presence of a polyamino group derived from a particular
polyamino compound, i.e., one in which there is one primary or
secondary amino group and at least one tertiary amine or nitrogen
heterocyclic moiety. Such polyamino groups, when present in the
nitrogen-containing esters of (B)(1) and optionally of (B)(2) in
the proportion stated above enhances the dispersability of such
esters in lubricant compositions and additive concentrates for
lubricant compositions.
Still another essential element of Component (B)(1) and optionally
(B)(2) is the extent of esterification in relation to the extent of
neutralization of the unesterified carboxy groups of the
carboxy-containing interpolymer through the conversion thereof to
polyamino-containing groups. For convenience, the relative
proportions of the high molecular weight ester group to the low
molecular weight ester group and to the polyamino group are
expressed in terms of molar ratios of (50-95):(5-50):0.1-15),
respectively. The preferred ratio is (70-85):(15-30):5. It should
be noted that the linkage described as the carbonyl-polyamino group
may be imide, amide, or amidine and inasmuch as any such linkage is
contemplated within the present invention, the term "carbonyl
polyamino" is thought to be a convenient, generic expression useful
for the purpose of defining the inventive concept. In a
particularly advantageous embodiment of the invention such linkage
is imide or predominantly imide.
Still another important element of Component (B) is the molecular
weight of the carboxy-containing interpolymer. For convenience, the
molecular weight is expressed in terms of the "inherent viscosity"
of the interpolymer which is a widely recognized means of
expressing the molecular size of a polymeric substance. As used
herein, the inherent viscosity is the value obtained in accordance
with the formula ##EQU1## wherein the relative viscosity is
measured in a dilution viscometer and is determined by dividing the
flow time of a solution of the interpolymer in 100 ml. of acetone,
by the flow time of acetone at 30.degree..+-.0.02.degree. C. For
purpose of computation by the above formula, the concentration is
the number of grams of the interpolymer per 100 ml. of acetone. The
unit of inherent viscosity is the deciliter per gram (dLg.sup.-1).
A more detailed discussion of inherent viscosity, as well as its
relationship to the average molecular weight of an interpolymer,
appears in Jan F. Rabek, Experimental Methods in Polymer Chemistry,
(1983 Edition), pages 126, et seq. (incorporated herein by
reference for purposes of describing and disclosing inherent
viscosity and means for determining such).
While interpolymers having an inherent viscosity of from about 0.05
to about 2 are contemplated in Component (B), the preferred
interpolymers are those having an inherent viscosity of from about
0.1 to about 1. In most instances, interpolymers having an inherent
viscosity of from about 0.1 to about 0.8 are particularly
preferred.
From the standpoint of utility, as well as for commercial and
economical reasons, mixed esters in which the high molecular weight
ester group has from 8 to 24 aliphatic carbon atoms, the low
molecular weight ester group has from 3 to 5 carbon atoms, and the
carbonyl polyamino group where required or optional is derived from
a primary-aminoalkyl-substituted tertiary amine, or heterocyclic
amine. Specific examples of the high molecular weight alkyl in the
carboxylic ester include heptyl, isooctyl, decyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl,
tricosyl, tetracosyl, etc. Specific examples of the low molecular
weight alkyl in the carboxylic ester include methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, n-pentyl,
neo-pentyl, n-hexyl, cyclohexyl, cyclopentyl, 2-methyl-butyl,
2,3-dimethyl-butyl, etc. In most instances, alkyl groups of
suitable size comprise the preferred high and low molecular weight
ester groups. Polar substituents may be present in such ester
groups. Examples of polar substituents are chloro, bromo, ether,
nitro, etc.
Examples of the carbonyl polyamino group include those derived from
polyamino compounds having one primary or secondary amino group and
at least one tertiary amine or nitrogen heterocyclic moiety such as
tertiary-amino or heterocyclic amino group. Such compounds may thus
be tertiary-amino substituted primary or secondary amines or other
substituted primary or secondary amines in which the substituent is
derived from pyrroles, pyrrolidones, caprolactams, oxazolidones,
oxazoles, thiazoles, pyrazoles, pyrazolines, imidazoles,
imidazolines, thiazines, oxazines, diazines, oxycarbamyl,
thiocarbamyl, uracils, hydantoins, thiohydantoins, guanidines,
ureas, sulfonamides, phosphoramides, phenothiazines, amidines, etc.
Examples of such polyamino compounds include
dimethylamino-ethylamine, dibutylamino-ethylamine,
3-dimethylamino-1-propylamine, 4-methylethylamino-1-butylamine,
pyridyl-ethylamine, N-morpholino-ethylamine,
tetrahydropyridyl-ethylamine, bis-(dimethylaminopropyl)amine,
bis-(diethylaminoethyl)amine, N,N-dimethyl-p-phenylene diamine,
piperidyl-ethylamine, 1-aminoethyl pyrazole,
1-(methylamino)pyrazoline, 1-methyl-4-amino-octyl pyrazole,
1-aminobutyl imidazole, 4-aminoethyl thiazole, 2-aminoethyl
pyridine, ortho-amino-ethyl-N,N-dimethylbenzenesulfamide,
N-aminoethyl phenothiazine, N-aminoethylacetamidine,
1-aminophenyl-2-aminoethyl pyridine,
N-methyl-N-aminoethyl-S-ethyl-dithiocarbamate, etc. Preferred
polyamino compounds include the N-aminoalkyl-substituted
morpholines such as aminopropyl morpholine. For the most part, the
polyamino compounds are those which contain only one primary-amino
or secondary-amino group and, preferably at least one
tertiary-amino group. The tertiary amino group is preferably a
heterocyclic amino group. In some instances polyamino compounds may
contain up to about 6 amino groups although, in most instances,
they contain one primary amino group and either one or two tertiary
amino groups. The polyamino compounds may be aromatic or aliphatic
amines and are preferably heterocyclic amines such as
amino-alkyl-substituted morpholines, piperazines, pyridines,
benzo-pyrroles, quinolines, pyrroles, etc. They are usually amines
having from 4 to about 30 carbon atoms, preferably from 4 to about
12 carbon atoms. Polar substituents may likewise be present in the
polyamines.
The carboxy-containing interpolymers include principally
interpolymers of alpha, beta-unsaturated acids or anhydrides such
as maleic anhydride or itaconic anhydride with olefins (aromatic or
aliphatic) such as ethylene, propylene, styrene, or isobutene. The
styrene-maleic anhydride interpolymers are especially useful. They
are obtained by polymerizing equal molar amounts of styrene and
maleic anhydride, with or without one or more additional
interpolymerizable comonomers. In lieu of styrene, an aliphatic
olefin may be used, such as ethylene, propylene or isobutene. In
lieu of maleic anhydride, acrylic acid or methacrylic acid or ester
thereof may be used. Such interpolymers are know in the art and
need not be described in detail here. Where an interpolymerizable
comonomer is contemplated, as in (B)(2), it should be present in a
relatively minor proportion, i.e., less that about 0.3 mole,
usually less than about 0.15 mole, per mole of either the olefin
(e.g. styrene) or the alpha, beta-unsaturated acid or anhydride
(e.g. maleic anhydride). Various methods of interpolymerizing
styrene and maleic anhydride are known in the art and need not be
discussed in detail here. For purpose of illustration, the
interpolymerizable comonomers include acrylic acid and methacrylic
acid, their alkyl esters, acrylamide and methacrylamide and their
N-substituted derivatives, itaconic acid and anhydride, citraconic
acid and anhydride, isobutylene, diisobutylene and higher
oligomers, t-butylstyrene and methylstyrene isomers.
Alpha-methylstyrene, acrylic and methacrylic esters are preferred;
esters of methacrylic acid are most preferred. Terpolymers of
styrene, maleic anhydride and esters of methacrylic acid are
preferred.
The carboxy-containing interpolymers are obtained by polymerization
of alpha, beta-unsaturated acids, anhydrides or esters thereof,
with a low molecular weight aliphatic olefin or styrene in a
suitable solvent. The temperature range for the reaction is from
the melting point of the reactants to the decomposition temperature
of the components, preferably from about 40.degree. C. to about
150.degree. C. The alpha, beta unsaturated acid or anhydride,
usually as a solution in aromatic solvent, is heated from ambient
temperature to the reaction temperature. A portion of a free
radical initiator is added at the reaction temperature. The
remainder of the free radical initiator and the low molecular
weight aliphatic olefin are added dropwise over about 20 to about
180 minutes. A vacuum, about 30 to about 760 torr, may be used to
control the reaction temperature by effecting reflux. The total
time of polymerization is usually from about 1 to about 8 hours.
The solvents employed provide a medium for polymerization as well
as contribute to the control of molecular weight of the
interpolymer by acting as a chain transfer agent, (e.g., act to
terminate the propagating free radical). Examples of solvents
suitable for the reaction are toluene, xylene, benzene and cumene.
The preferred solvents are xylene and toluene; most preferred is
toluene.
The free radical initiator should decompose to provide enough free
radicals to form the interpolymers. Polymerization conditions are
chosen such that the half life of a free radical initiator is from
about 0.3 about 2 hours, with 0.5 to 1 hour preferred. An example
of a suitable initiator is benzoyl peroxide, although other
peroxides, peresters and azo initiators may be employed.
The addition time of the low molecular weight aliphatic olefin or
styrene monomer controls the molecular weight. For faster addition
of this monomer, the molecular weight is higher. Therefore, it is
preferred that this monomer is added over about 30 to about 120
minutes, and most preferred over 45-100 minutes. A portion of the
free radical initiator is added at reaction temperature immediately
before addition of the low molecular weight aliphatic olefin or
styrene monomer. This initial portion is from one-fourth to
three-fourths of the total amount of the initiator. Preferably,
one-half of the initiator is added before the low molecular weight
aliphatic olefin or styrene monomer addition is begun. The addition
time for the remainder of the free radical initiator is usually the
same as the addition time of the low molecular weight aliphatic
olefin or styrene monomer.
The process with the interpolymerizable comonomers is essentially
the same as above. The interpolymerizable comonomer may be added
with the alpha, beta-unsaturated carboxylic acid, anhydride or
ester thereof or may be mixed with the low molecular weight
aliphatic olefin or styrene monomer or with the free radical
initiator. When the comonomer has little tendency to
homopolymerize, it may be added with the alpha, beta-unsaturated
carboxylic acid, anhydride or ester thereof as well as with the
free radical initiator or low molecular weight aliphatic olefin or
styrene monomer. Itaconic and citraconic acids and anhydrides are
examples of comonomers of this type. Comonomers which have a
tendency to homopolymerize should be added along with either the
free radical initiator or the low molecular weight aliphatic olefin
or styrene monomer.
The mixed esters of Component (B) are most conveniently prepared by
first esterifying the carboxy-containing interpolymer with a
relatively high molecular weight alcohol and a relatively low
molecular weight alcohol to convert at least about 50% and no more
than about 98% of the carboxy radicals of the interpolymer to ester
radicals and then neutralizing the remaining carboxy radicals with
a polyamino compound as in (B)(1) or optionally as in (B)(2) such
as described above. To incorporate the appropriate amounts of the
two alcohol groups into the interpolymer, the ratio of the high
molecular weight alcohol to the low molecular weight alcohol used
in the process should be within the range of from about 2:1 to
about 9:1 on a molar basis. In most instances the ratio is from
about 2.5:1 to about 5:1. More than one high molecular weight
alcohol or low molecular weight alcohol may be used in the process;
so also may be used commercial alcohol mixtures such as the
so-called Oxoalcohols which comprise, for example mixtures of
alcohols having from 8 to about 24 carbon atoms. A particularly
useful class of alcohols are the commercial alcohols or alcohol
mixtures comprising decylalcohol, dodecyl alcohol, tridecyl
alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol
and octadecyl alcohol. Other alcohols useful in the process are
illustrated by those which, upon esterification, yield the ester
groups exemplified above.
The extent of esterification, as indicated previously, may range
from about 50% to about 98% conversion of the carboxy radicals of
the interpolymer to ester radicals. In a preferred embodiment, the
degree of esterification ranges from about 5% to about 95%.
The esterification can be accomplished simply by heating the
carboxy-containing interpolymer and the alcohol or alcohols under
conditions typical for effecting esterification. Such conditions
usually include, for example, a temperature of at least about
80.degree. C., preferably from about 150.degree. C. to about
250.degree. C., provided that the temperature be below the
decomposition point of the reaction mixture, and the removal of
water of esterification as the reaction proceeds. Such conditions
may optionally include the use of an excess of the alcohol reactant
so as to facilitate esterification, the use of a solvent or diluent
such as mineral oil, toluene, benzene, xylene or the like and a
esterification catalyst such as toluene sulfonic acid, sulfuric
acid, aluminum chloride, boron trifluoride-triethylamine,
hydrochloric acid, ammonium sulfate, phosphoric acid, sodium
methoxide or the like. These conditions and variations thereof are
well know in the art.
A particularly desirable method of effecting esterification
involves first reacting the carboxy-containing interpolymer with
the relatively high molecular weight alcohol and then reacting the
partially esterified interpolymer with the relatively low molecular
weight alcohol. A variation of this technique involves initiating
the esterification with the relatively high molecular weight
alcohol and before such esterification is complete, the relatively
low molecular weight alcohol is introduced into the reaction mass
so as to achieve a mixed esterification. In either event it has
been discovered that a two-step esterification process whereby the
carboxy-containing interpolymer is first esterified with the
relatively high molecular weight alcohol so as to convert from
about 50% to about 75% of the carboxy radicals to ester radicals
and then with the relatively low molecular weight alcohol to
achieve the finally desired degree of esterification results in
products which have unusually beneficial viscosity properties.
The esterified interpolymer is then treated with a polyamino
compound as in (B)(1) or optionally as in (B)(2) in an amount so as
to neutralize substantially all of the unesterified carboxy
radicals of the interpolymer. The neutralization is preferably
carried out at a temperature of at least about 80.degree. C., often
from about 120.degree. C. to about 250.degree. C., provided that
the temperature does not exceed the decomposition point of the
reaction mass. In most instances the neutralization temperature is
between about 150.degree. C. and 250.degree. C. A slight excess of
the stoichiometric amount of the polyamino compound is often
desirable, so as to insure substantial completion of
neutralization, i.e., no more than about 2% of the carboxy radicals
initially present in the interpolymer remained unneutralized.
The following examples are illustrative of the preparation of
Component (B) of the present invention. Unless otherwise indicated
all parts and percentages are by weight.
EXAMPLE (B)(1)-1
A styrene-maleic anhydride copolymer is obtained by preparing a
solution of styrene (16.3 parts by weight) and maleic anhydride
(12.9 parts) in a benzene-toluene solution (270 parts; weight ratio
of benzene:toluene being 66.5:33.5 ) and contacting the solution at
86.degree. C. in nitrogen atmosphere for 8 hours with a catalyst
solution prepared by dissolving 70% benzoyl peroxide (0.42 part) in
a similar benzene-toluene mixture (2.7 parts). The resulting
product is a thick slurry of the interpolymer in the solvent
mixture. To the slurry there is added mineral oil (141 parts) while
the solvent mixture is being distilled off at 150.degree. C. and
then at 150.degree. C./200 mm Hg. To 209 parts of the stripped
mineral oil-interpolymer slurry (the copolymer having an inherent
viscosity of 0.72) there are added toluene (25.2 parts), n-butyl
alcohol (4.8 parts), a commercial alcohol consisting essentially of
primary alcohols having from 12 to 18 carbon atoms of primary
alcohols having from 12 to 18 carbon atoms (56.6 parts) and a
commercial alcohol consisting of primary alcohols having from 8 to
10 carbon atoms (10 parts) and to the resulting mixture there is
added 96% sulfuric acid (2.3 parts). The mixture is then heated at
150.degree.-160.degree. C. for 20 hours whereupon water is
distilled off. An additional mount of sulfuric acid (0.18 part)
together with an additional amount of n-butyl alcohol (3 parts) is
added and the esterification is continued until 95% of the carboxy
radicals of the polymer has been esterified. To the esterified
copolymer, there is then added aminopropyl morpholine (3.71 parts;
10% in excess of the stoichiometric amount required to neutralize
the remaining free carboxy radicals) and the resulting mixture is
heated to 150.degree.-160.degree. C./10 mm. Hg to distill off
toluene and any other volatile components. The stripped product is
mixed with an additional amount of mineral oil (12 parts) filtered.
The filtrate is a mineral oil solution of the nitrogen-containing
mixed ester having a nitrogen content of 0.16-0.17%.
EXAMPLE (B)(1)-2
The procedure of Example (B)(1)-1 is followed except that the
esterification is carried out in two steps, the first step being
the esterification of the styrene-maleic anhydride copolymer with
the commercial alcohols having from 8 to 18 carbon atoms and the
second step being the further esterification of the copolymer with
n-butyl alcohol.
EXAMPLE (B)(1)-3
The procedure of Example (B)(1)-1 is followed except that the
esterification is carried out by first esterifying the
styrene-maleic anhydride copolymer with the commercial alcohol
having from 8 to 18 carbon atoms until 70% of the carboxyl radicals
of the copolymer have been converted to ester radicals and
thereupon continuing the esterification with any yet-unreacted
commercial alcohols and n-butyl alcohol until 95% of the carbonyl
radicals of the interpolymer have been converted to ester
radicals.
EXAMPLE (B)(1)-4
The procedure of Example (B)(1)-1 is followed except that the
copolymer is prepared by polymerizing a solution consisting of
styrene (416 parts), maleic anhydride (392 parts), benzene (2153
parts) and toluene (5025 parts) in the presence of benzoyl peroxide
(1.2 parts) at 65.degree.-106.degree. C. (The resulting copolymer
has an inherent viscosity of 0.42).
EXAMPLE (B)(1)-5
The procedure of Example (B)(1)-1 is followed except that the
styrene-maleic anhydride copolymer is obtained by polymerizing a
mixture of styrene (416 parts), maleic anhydride (392 parts),
benzene (6101 parts) and toluene (2310 parts) in the presence of
benzoyl peroxide (1.2 parts) at 78.degree.-92.degree. C. (The
resulting copolymer has an inherent viscosity of 0.91).
EXAMPLE (B)(1)-6
The procedure of Example (B)(1)-1 is followed except that the
styrene-maleic anhydride copolymer is prepared by the following
procedure: Maleic anhydride (392 parts) is dissolved in benzene
(6870 parts). To this mixture there is added styrene (416 parts) at
76.degree. C. whereupon benzoyl peroxide (1.2 parts) is added. The
polymerization mixture is maintained at 80.degree.-82.degree. C.
for about 5 hours. (The resulting copolymer has an inherent
viscosity of 1.24.)
EXAMPLE (B)(1)-7
The procedure of Example (B)(1)-1 is followed except that acetone
(1340 parts) is used in place of benzene as the polymerization
solvent and that azobisisobutyronitrile (0.3 part) is used in place
of benzoyl peroxide as a polymerization catalyst.
EXAMPLE (B)(1)-8
A copolymer (0.86 carboxyl equivalent) of styrene and maleic
anhydride (prepared from an equal molar mixture of styrene and
maleic anhydride and having an inherent viscosity of 0.69) is mixed
with mineral oil to form a slurry, and then esterified with a
commercial alcohol mixture (0.77 mole; comprising primary alcohols
having from 8 to 18 carbon atoms) at 150.degree.-160.degree. C. in
the presence of a catalytic amount of sulfuric acid until about 70%
of the carboxyl radicals are converted to ester radicals. The
partially esterified copolymer is then further esterified with a
n-butyl alcohol (0.31 mole) until 95% of the carboxyl radicals of
the copolymer are converted to the mixed ester radicals. The
esterified copolymer is then treated with aminopropyl morpholine
(slight excess of the stoichiometric amount to neutralize the free
carboxyl radicals of the copolymer) at 150.degree.-160.degree. C.
until the resulting product is substantially neutral (acid number
of 1 to phenolphthalein indicator). The resulting product is mixed
with mineral oil so as to form an oil solution containing 34 % of
the polymeric product.
Examples (B)(1)-1 through (B)(1)-8 are prepared using mineral oil
as the diluent. All of the mineral oil or a portion thereof may be
replaced with a naturally occurring triglyceride. The preferred
triglyceride is rapeseed oil or the high oleic sunflower oil.
EXAMPLE (B)(1)-9
Charged to a 12 liter 4 neck flask is 3621 parts of the copolymer
of Example (B)(1)-8 as a toluene slurry. The percent toluene is
about 76 percent. Stirring is begun and 933 parts (4.3 equivalents)
Alfol 1218 alcohol and 1370 parts xylene are added. The contents
are heated and toluene is removed by distillation. Additional
xylene is added in increments of 500, 500, 300 and 300 parts while
continuing to remove toluene, the object being to replace the lower
boiling toluene with the higher boiling xylene. The removal of
solvent is stopped when the temperature of 140.degree. C. is
reached. The flask is then fitted with an addition funnel and the
condenser is set to reflux. At 140.degree. C., 23.6 parts (0.17
equivalents) methanesulfonic acid in 432 parts (3 equivalents)
Alfol 810 alcohol is added in about 20 minutes. The contents are
stirred overnight at reflux while collecting water in a Dean Stark
trap. Then added is 185 parts (2.5 equivalents) of n-butanol
containing therein 3.0 parts (0.02 equivalents) of methanesulfonic
acid. This addition occurs over a 60 minute time period. The
contents are maintained at reflux for 8 hours and then an
additional 60 parts (0.8 equivalents) n-butanol is added and the
contents are permitted to reflux overnight. At 142.degree. C. is
added 49.5 parts (0.34 equivalents) aminopropylmorpholine in 60
minutes. After a 2 hour reflux 13.6 parts (equivalents) 50% aqueous
sodium hydroxide is added over 60 minutes and after an additional
60 minutes of stirring there is added 17 parts of an alkylated
phenol comprising 75% 2,b-di-t-butylphenol, 15%
2,4,6-tri-t-butylphenol and 10% ortho-t-butylphenol.
To a 1 liter flask is added 495 parts of the above esterified
product. The contents are heated to 140.degree. C. and 337 parts
Sunyl.RTM. 80 is added. Solvent is removed at 155.degree. C. with
nitrogen blowing at 1 cubic foot per hour. The final stripping
conditions are 155.degree. C. and 20 mm Hg. At 100.degree. C. the
contents are filtered using diatomaceous earth to give a product
containing 0.3% alkylated phenol and 67% Sunyl.RTM. 80.
EXAMPLE (B)(1)-10
The procedure of Example (B)(1)-9 is followed except that RS80 is
utilized instead of Sunyl 80. The RS80 content is 57% and the
alkylated phenol content is 0.3%.
EXAMPLE (B)(2)-1
Mix and heat 490 parts of maleic anhydride and 6900 parts of
toluene to 100.degree. C. Prepare an initiator solution by mixing
14.3 parts of 70% benzoyl peroxide and 500 parts of toluene. Add
one-half of the initiator solution to the maleic anhydride and
toluene at about 100.degree. C. Charge the remainder of the
initiator solution and a mixture of 494 parts of styrene, 29.5
parts of alpha-methyl styrene and 25 parts of methyl methacrylate
dropwise over 90 minutes at a constant rate. Apply a vacuum to
obtain reflux at 100.degree. C. Maintain the reaction temperature
at 100.degree. C. for 4 hours. The interpolymer obtained should
have an inherent viscosity of 0.14 dLg.sup.-1.
Charge to a suitable vessel a toluene slurry (1688 parts) having
12.32% solids and 87.68% volatiles of the interpolymer, Alfol 1218
(217 parts) and mineral oil (130 parts). Heat the mixture to
100.degree. C. with medium agitation under nitrogen. Add sulfuric
acid (4.22 parts of a 93% solution) and Alfol 810 (101 parts) to
the mixture. Heat the mixture to 150.degree. C. by removing
toluene-water distillate. Add butanol (20 parts) to the mixture.
Maintain the temperature of the mixture at 150.degree. C. for 11/2
hours. Add a second portion of butanol (20 parts) to the mixture.
Maintain the temperature of the mixture at 150.degree. C. until the
net acid number indicates that esterification is at least 95%
complete. Add 15 parts aminopropylmorpholine and di-tert-butyl
phenol (1.04 parts) to the mixture. Vacuum strip the mixture at
150.degree. C. and 100 torr. Add a second portion of di-tert-butyl
phenol (1.04 parts) along with diatomaceous earth (16 parts). Cool
the mixture to 100.degree. C. and filter through a hot funnel to
yield the desired product.
EXAMPLE (B)(2)-2
Utilizing the same procedure as described in Example (B)(2)-1,
polymerize 490 parts of maleic anhydride with 520 parts of styrene
and 25 parts of methyl methacrylate. Use 11.5 parts of benzoyl
peroxide along with 7400 parts of toluene. The interpolymer
obtained should have an inherent viscosity of 0.13 dLg.sup.-1.
Esterify this interpolymer utilizing the procedure described in
Example (B)(2)-1. Use 257 parts of Alfol 1218, 45.2 parts of Alfol
810, 134 parts of a mineral oil, 54 parts butanol, 15 parts of
aminopropylmorpholine, 2.08 parts of di-tert-butyl phenol and 16
parts of diatomaceous earth. Replace the sulfuric acid of Example
(B)(2)-1 with 5.46 parts of a 70% solution of methanesulfonic
acid.
EXAMPLE (B)(2)-3
Utilizing the same procedure as described in Example (B)(2)-1,
polymerize 490 parts of maleic anhydride with 520 parts of styrene
and 50 parts of methyl methacrylate. Use 8.5 parts of benzoyl
peroxide along with 7400 parts of toluene. The interpolymer
obtained should have an inherent viscosity of 0.15 dLg.sup.-1.
Esterify 212 parts of this interpolymer according to the procedure
as described in Example(B)(2)-1, except use 5.46 parts of a 70%
solution of methanesulfonic acid in place of sulfuric acid. Use 278
parts of Alfol 1218, 49 parts of Alfol 810, 136 parts of a mineral
oil, 54 parts of butanol, 15 parts of aminopropylmorpholine, 2.08
parts of di-tert-butyl phenol; and 16 parts of diatomaceous
earth.
EXAMPLE (B)(2)-4
Mix and heat 490 parts of maleic anhydride and 6900 parts of
toluene to 100.degree. C. Prepare an initiator solution by mixing
14.3 parts of 70% benzoyl peroxide and 500 parts of toluene. Add
one-half of the initiator solution to the maleic anhydride and
toluene at about 100.degree. C. Charge the remainder of the
initiator solution and a mixture of 494 parts of styrene, 29.5
parts of alpha-methyl styrene and 25 parts of methyl methacrylate
dropwise over 90 minutes. Apply a vacuum to obtain reflux at
100.degree. C. Maintain the reaction temperature at 100.degree. C.
for 4 hours. The interpolymer obtained should have an inherent
viscosity of 0.14 dLg.sup.-1. Charge to a suitable vessel a toluene
slurry (1688 parts) having 12.32% solids and 87.68% volatiles of
this interpolymer, Alfol 1218 (257 parts) and mineral oil (130
parts). Heat the mixture to 100.degree. C. with medium agitation
under nitrogen. Add sulfuric acid (4.22 parts of a 93% solution)
and Alfol 810 (45 parts) to the mixture. Heat the mixture to
150.degree. C. by removing toluene-water distillate. Add butanol
(27 parts) to the mixture. Maintain the temperature of the mixture
at 150.degree. C. for 11/2 hours. Add a second portion of butanol
(27 parts) to the mixture. Maintain the temperature of the mixture
at 150.degree. C. until the net acid number indicates that
esterification is at least 95% complete. Add sodium hydroxide (1.44
parts of a 50% aqueous solution) and Isonox 133 (1.04 parts) to the
mixture. Vacuum strip the mixture at 150.degree. C. and 100 torr.
Add a second portion of Isonox 133 (1.04 parts) along with
diatomaceous earth (16 parts). Cool the mixture to 100.degree. C.
and filter through a hot funnel to yield the desired product.
EXAMPLE (B)(2)-5
Mix and heat 490 parts of maleic anhydride and 6900 parts of
toluene to 100.degree. C. Prepare an initiator solution by mixing
14.3 parts of 70% benzoyl peroxide with 500 parts of toluene. Add
one-half of the initiator solution to the maleic anhydride/toluene
mixture. Apply a vacuum to obtain reflux at 100.degree. C. Add the
remainder of the initiator solution and a mixture of 494 parts of
styrene and 59 parts of alpha-methyl styrene dropwise over 90
minutes. Maintain the reaction temperature at 100.degree. C. for 4
hours. The interpolymer obtained should have an inherent viscosity
of 0.15 dLg.sup.-1. Esterify 208 parts of this interpolymer by the
same procedure as Example (B)(2)-4. Use 257 parts of Alfol 1218, 45
parts of Alfol 810, 130 parts of mineral oil, 4.22 parts of a 93%
solution of sulfuric acid, 54 parts of butanol, 1.28 parts of 50%
aqueous solution of sodium hydroxide, 2 parts of Isonox 133 and 16
parts of diatomaceous earth.
EXAMPLE (B)(3)-1
Heat 490 parts of maleic anhydride and 5000 parts of toluene to
100.degree. C. Prepare an initiator solution by mixing 2.13 parts
of benzoyl peroxide and 500 parts of toluene. One-half of this
solution is to be added all at once. Add 520 parts styrene and the
remaining initiator solution dropwise over 40 minutes. Maintain the
reaction temperature at 100.degree. C. for 4 hours. The
interpolymer obtained should have an inherent viscosity at
30.degree. C. (1 gram/100 mls acetone) of about 0.30 dLg.sup.-1.
Charge a vessel with a toluene slurry (870 parts) having 15.5%
solids and 84.5% volatiles of this interpolymer and Alfol 1218 (278
parts). Heat the mixture to 100.degree. C. under nitrogen with
medium agitation. Add sulfuric acid (3.1 parts of a 96% solution in
water) and 48.7 parts of Alfol 810 to the vessel. Raise the
temperature of the mixture to 145.degree. C.-150.degree. C. by
removing toluene-water distillate. Add 301 parts of a mineral oil
150.degree. C. Maintain the temperature of the mixture at
145.degree. C.-150 C. until net acid number indicates that
esterification is at least 75% complete. Add 26.7 parts of
n-butanol dropwise over 15 minutes. Maintain the temperature of the
mixture at 145.degree. C.-150 C. for 3 hours. Add solution of
sulfuric acid (0.52 parts of a 96% solution) and 26.7 parts of
butanol dropwise over 10 minutes. Maintain the temperature of the
mixture at 145.degree. C.-150.degree. C. until the net acid number
indicates that the esterification is at least 95% complete. Add
sodium hydroxide (0.96 parts of a 50% aqueous solution) to the
mixture, and add Ethyl Antioxidant 733 (1.36 parts) to the mixture.
Vacuum strip the mixture at 155.degree. C. and 5 torr. Add
diatomaceous earth (10 parts) to the mixture along with Ethyl
Antioxidant 733 (1.36 parts). Cool the mixture to 100.degree. C.
and filter through a heated funnel to yield the desired
product.
EXAMPLE (B)(3)-2
Esterify a toluene slurry (928 parts) having 15.5% solids and 84.5%
volatiles of the interpolymer of Example (B)(3)-1 utilizing the
same procedure as Example (B)(3)-1. Use 348 parts Alfol 1218, 61
parts Alfol 810, 4.53 parts of a 96% sulfuric acid solution, 293
parts of a mineral oil, 66.6 parts of butanol, 1.46 parts of Ethyl
Antioxidant 733 and 109 parts of diatomaceous earth.
EXAMPLE (B)(3)-3
Mix and heat 490 parts of maleic anhydride and 5000 parts of xylene
to 100.degree. C. Prepare an initiator solution by mixing 17 parts
of 70% benzoyl peroxide with 500 parts of xylene. Add the initiator
solution in one portion at 100.degree. C. Apply a vacuum to affect
reflux. At 100.degree. C. add 520 parts of styrene over 20 minutes.
The reaction is very exothermic. Maintain the reaction temperature
at 100.degree. C. for 4 hours after the addition is completed. The
interpolymer obtained should have an inherent viscosity of 0.15
dLg.sup.-1. Charge to a suitable vessel this interpolymer (404
parts) and Alfol 1218 (555 parts). Heat the mixture to 100.degree.
C. with agitation under nitrogen. Add Alfol 810 (98 parts) and 70%
methanesulfonic acid (6.4 parts) to the mixture. Raise the
temperature to 150.degree. C. by removal of water-xylene
distillate. Maintain the temperature of the mixture at 150.degree.
C. until net acid number indicates that esterification is at least
75% complete. Add butanol (104 parts) dropwise to the mixture.
Maintain the temperature of the mixture at 150.degree. C. until the
net acid number indicates that esterification is at least 95%
complete. Add Ethyl Antioxidant 733 (4.6 parts) and sodium
hydroxide (2 parts of a 50% aqueous solution) to the mixture.
Vacuum strip the mixture at 150.degree. C. and 20 torr. Cool the
mixture to 100.degree. C. and add Ethyl Antioxidant 733 (4.6 parts)
and diatomaceous earth (36 parts) to the mixture. Filter the
mixture through a heated funnel to yield the desired product.
EXAMPLE (B)(3)-4
Heat 490 parts of maleic anhydride and 5000 parts of toluene to
60.degree. C. Prepare an initiator solution by mixing 0.5 parts of
Percadox 16 (4-t-butylcyclohexyl peroxy dicarbonate from Noury
Chemical Company) and 500 parts of toluene. One-half of this
solution is to be added all at once. Add the styrene and the
remaining initiator solution dropwise over 40 minutes. Maintain the
reaction temperature at 60.degree. C. for 4 hours. The interpolymer
obtained should have an inherent viscosity at 30.degree. C. (1
gram/100 mls acetone) of about 1.5 dLg.sup.-1. Esterify this
interpolymer by the same procedure as (B)(3)-3. Use 257 parts of
Alfol 1218, 45 parts of Alfol 810, 130 parts of a mineral oil, 4.2
parts of a 93% sulfuric acid solution, 54 parts butanol, 1.21 parts
of a 50% aqueous sodium hydroxide solution, 2 parts of Isonox 133
and 16 parts of diatomaceous earth.
EXAMPLE (B)(3)-5
Heat 490 parts of maleic anhydride and 5000 parts of toluene to
60.degree. C. Prepare an initiator solution by mixing 1.0 parts of
Percadox 16 with 500 parts of toluene. One-half of the initiator
solution is to be added to the maleic anhydride and toluene
solution at 60.degree. C. Add 520 parts of styrene and the
remainder of the initiator solution dropwise over 60 minutes.
Maintain temperature at about 60.degree. C. for 4 hours by applying
a vacuum to affect reflux. The interpolymer obtained should have an
inherent viscosity of 0.8 dLg.sup.-1. Esterify this interpolymer by
the procedure utilized in Example (B)(3)-3. Use 278 parts of Alfol
1218, 49 parts of Alfol 810, 362 parts of a mineral oil, 4.21 parts
of a 93% sulfuric acid solution, 54 parts butanol, 1.28 parts of a
50% aqueous sodium hydroxide solution, 1.72 parts of Isonox 133 and
20 parts of diatomaceous earth.
In addition to components (A) and (B) the compositions of this
invention may also include (C) a synthetic ester base oil.
(C) The Synthetic Ester Base Oil
The synthetic ester base oil comprises the reaction of a
monocarboxylic acid of the formula
a dicarboxylic acid of the formula ##STR5## or an aryl carboxylic
acid of the formula
wherein R.sup.4 is a hydrocarbyl group containing from about 4 to
about 24 carbon atoms, R.sup.5 is hydrogen or a hydrocarbyl group
containing from about 4 to about 50 carbon atoms, R.sup.6 is
hydrogen or a hydrocarbyl group containing from 1 up to about 24
carbon atoms, m is an integer of from 0 to about 6, and p is an
integer of from 1 to 4; with an alcohol of the formula ##STR6##
wherein R.sup.7 is an aliphatic group containing from 1 to about 24
carbon atoms or an aromatic group containing from 6 to about 18
carbon atoms, R.sup.14 is hydrogen or an alkyl group containing 1
or 2 carbon atoms, t is from 0 to about 40 and n is from 1 to about
6.
Within the monocarboxylic acid, R.sup.4 preferably contains from
about 6 to about 18 carbon atoms. An illustrative but
non-exhaustive list of monocarboxylic acids are the isomeric
carboxylic acids of butanoic, hexanoic, octanoic, nonanoic,
decanoic, undecanoic, dodecanoic, palmitic, and stearic acids.
Within the dicarboxylic acid, R.sup.5 preferably contains from
about 4 to about 24 carbon atoms and m is an integer of from 1 to
about 3. An illustrative but non-exhaustive list of dicarboxylic
acids are succinic, glutaric, adipic, pimelic, suberic, azelaic,
sebacic, maleic, and fumaric acids.
As aryl carboxylic acids, R.sup.6 preferably contains from about 6
to about 18 carbon atoms and p is 2. Aryl carboxylic acids having
utility are benzoic, toluic, ethylbenzoic, phthalic, isophthalic,
terephthalic, hemimellitic, trimellitic, trimeric, and pyromellitic
acids.
Within the alcohols, R.sup.7 preferably contains from about 3 to
about 18 carbon atoms and t is from 0 to about 20. The alcohols may
be monohydric, polyhydric or alkoxylated monohydric and polyhydric.
Monohydric alcohols can comprise, for example, primary and
secondary alcohols. The preferred monohydric alcohols, however are
primary aliphatic alcohols, especially aliphatic hydrocarbon
alcohols such as alkenols and alkanols. Examples of the preferred
monohydric alcohols from which R.sup.7 is derived include
1-octanol, 1-decanol, 1-dodecanol, 1-tetradeconal, 1-hexadecanol,
1-octadecanol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol,
phytol, myricyl alcohol lauryl alcohol, myristyl alcohol, cetyl
alcohol, stearyl alcohol, and behenyl alcohol.
Examples of polyhydric alcohols are those containing from 2 to
about 6 hydroxy groups. They are illustrated, for example, by the
alkylene glycols such as ethylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol, dipropylene glycol,
tripropylene glycol, dibutylene glycol, tributylene glycol, and
other alkylene glycols. A preferred class of alcohols suitable for
use in this invention are those polyhydric alcohols containing up
to about 12 carbon atoms. This class of alcohols includes glycerol,
erythritol, pentaerythritol, dipentaerythritol, gluconic acid,
glyceraldehyde, glucose, arabinose, 1,7-heptanediol,
2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol,
1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol,
1,2,4-butanetriol, quinic acid, 2,2,6,6-tetrakis (hydroxymethyl)
cyclohexanol, 1-10-decanediol, digitaloal, and the like.
Another preferred class of polyhydric alcohols for use in this
invention are the polyhydric alcohols containing 3 to 10 carbon
atoms and particularly those containing 3 to 6 carbon atoms and
having at least three hydroxyl groups. Such alcohols are
exemplified by a glycerol, erythritol, pentaerythritol, mannitol,
sorbitol, 2-hydroxymethyl-2-methyl-1,3,propanediol
(trimethylolpropane), bis-trimethylolpropane, 1,2,4-hexanetriol and
the like.
The alkoxylated alcohols may be alkoxylated monohydric alcohols or
alkoxylated polyhydric alcohols. The alkoxy alcohols are generally
produced by treating an alcohol with an excess of an alkylene oxide
such as ethylene oxide or propylene oxide. For example, from about
6 to about 40 moles of ethylene oxide or propylene oxide may be
condensed with an aliphatic alcohol.
In one embodiment, the aliphatic alcohol contains from about 14 to
about 24 carbon atoms and may be derived from long chain fatty
alcohols such as stearyl alcohol or oleyl alcohol.
The alkoxy alcohols useful in the reaction with the carboxylic
acids to prepare synthetic esters are available commercially under
such trade names as "TRITON.RTM.", "TERGITOL.RTM." from Union
Carbide, "ALFONIC.RTM." from Vista Chemical, and "NEODOL.RTM." from
Shell Chemical Company. The TRITON.RTM. materials are identified
generally as polyethoxylated alkyl phenols which may be derived
from straight chain or branched chain alkyl phenols. The
TERGITOLS.RTM. are identified as polyethylene glycol ethers of
primary or secondary alcohols; the ALFONIC.RTM. materials are
identified as ethyoxylated linear alcohols which may be represented
by the general structure formula
wherein x varies between 4 and 16 and n is a number between about 3
and 11. Specific examples of ALFONIC.RTM. ethoxylates characterized
by the above formula include ALFONIC.RTM. 1012-60 wherein x is
about 8 to 10 and n is an average of about 5.7; ALFONIC.RTM.
1214-70 wherein x is about 10-12 and n is an average of about 10.6;
ALFONIC.RTM. 1412-60 wherein x is from 10-12 and n is an average of
about 7; and ALFONIC.RTM. 1218-70 wherein x is about 10-16 and n is
an average of about 10.7.
The NEODOL.RTM. ethoxylates are ethoxylated alcohols wherein the
alcohols are a mixture of linear and branched alcohols containing
from 9 to about 15 carbon atoms. The ethoxylates are obtained by
reacting the alcohols with an excess of ethylene oxide such as from
about 3 to about 12 or more moles of ethylene oxide per mole of
alcohol. For example, NEODOL.RTM. ethoxylate 23-6.5 is a mixed
linear and branched chain alcoholate of 12 to 13 carbon atoms with
an average of about 6.5 ethoxy units.
As stated above, the synthetic ester base oil comprises reacting
any above-identified acid or mixtures thereof with any
above-identified alcohol or mixtures thereof at a ratio of 1 COOH
per 1 OH group using esterification procedures, conditions and
catalysts known in the art.
A non-exhaustive list of companies that produce synthetic esters
and their trade names are BASF as Glissofluid, Ciba-Geigy as
Reolube, JCI as Emkarote, Oleofina as Radialube and the Emery Group
of Henkel Corporation as Emery.
The compositions of this invention, components (A) and (B) or
components. (A), (B) and (C) may further contain
(D) an antioxidant selected from the group consisting of
(1) a phenol of Formula I ##STR7## wherein R.sup.8 is hydrogen or a
hydrocarbyl group containing from 1 up to about 24 carbon atoms and
a is an integer of from 1 up to 5, q is an integer of from 1 up to
3 with the proviso that the sum of a and q does not exceed 6, or an
alkyl phenol of Formula II ##STR8## wherein R.sup.8 is an alkyl
group containing from 1 up to about 24 carbon atoms, X is a sulfur
or methylene, a is an integer of from 1 up to 4, b is an integer of
from 0 up to about 10 and c is an integer of from 1 up to 3;
(2) an aromatic amine of the formula ##STR9## wherein R.sup.9 is
##STR10## and R.sup.10 and R.sup.11 are independently a hydrogen or
an alkyl group containing from 1 up to about 24 carbon atoms and d
is 0 or 1; and
(3) a phosphite ester of the formula ##STR11## wherein each of
R.sup.12 and R.sup.13 is an alkyl group containing from 1 up to
about 24 carbon atoms.
(D)(1) The Phenols of Formula I and Formula II
Within this formula, R.sup.8 preferably contains from 1 up to about
8 carbon atoms, q is 1, and a is from 1 up to about 3.
Within this formula, R.sup.8 preferably contains from 1 up to about
8 carbon atoms, a is from 1 up to about 3, b is from 1 up to about
4 and C is 1 or 2. When x is sulfur, the phenol of Formula II is
made by sulfurizing a phenol with a sulfurizing agent such as
sulfur, a sulfur halide, or sulfide or hydrosulfide salt.
Techniques for making these sulfurized phenates are described in
U.S. Pat. Nos. 2,680,096; 3,036,971; and 3,775,321 which are hereby
incorporated by reference for their disclosures in this regard.
When x is methylene, the phenol of Formula II is made by reacting a
phenol with formaldehyde in the presence of an acid or basic
catalyst. Such linked phenates as well as sulfurized phenates are
described in detail in U.S. Pat. No. 3,350,038; particularly
columns 6-8 thereof, which is hereby incorporated by reference for
its disclosure in this regard.
(D)(2) The Aromatic Amine
Within the aromatic amine, preferably R.sup.9 is, ##STR12## and
R.sup.10 and R.sup.11 are alkyl groups. In a particularly
advantageous embodiment, the aromatic amine is a
nonylateddiphenylamine of the formula ##STR13## (D)(3) The
Phosphite Ester
Within the phosphite ester, R.sup.12 and R.sup.13 are preferably
from 4 to 12 carbon atoms and most preferably from 8 to 10 carbon
atoms.
The R.sup.12 and R.sup.13 groups may comprise a mixture of alkyl
groups derived from commercial alcohols. Examples of some preferred
monohydric alcohols and alcohol mixtures include the commercially
available "Alfol" alcohols marketed by Vista Chemical. Alfol 810 is
a mixture containing alcohols consisting essentially of
straight-chain, primary alcohols having 8 and 10 carbon atoms.
Alfol 12 is a mixture comprising mostly C.sub.12 fatty alcohols.
Alfol 1218 is a mixture of synthetic, primary, straight-chain
alcohols having 12 to 18 carbon atoms. The Alfol20+ alcohols are
mostly, on an alcohol basis, C.sub.20 alcohols as determined by GLC
(gas-liquid-chromatography). The Alfol 22+ alcohols are C.sub.18-28
primary alcohols having mostly, on an alcohol basis, C.sub.22
alcohols. These Alfol alcohols can contain a fairly large
percentage (up to 40% by weight) of paraffinic compounds which can
be removed before the reaction if desired.
Another example of a commercially available alcohol mixture is Adol
60 which comprises about 75% by weight of a straight-chain C.sub.22
primary alcohol, about 15% of a C.sub.20 primary alcohol and about
8% of C.sub.18 and C.sub.24 alcohols. Adol 320 comprises
predominantly oleyl alcohol. The Adol alcohols are marketed by
Sherex Corporation.
A variety of mixtures of monohydric fatty alcohols derived from
naturally occurring triglycerides and ranging in chain length of
from C.sub.8 to C.sub.18 are available from Procter & Gamble
Company. These mixtures contain various amounts of fatty alcohols
containing mainly 12, 14, 16, or 18 carbon atoms. For example,
CO-1214 is a fatty alcohol mixture containing 0.5 of C.sub.10
alcohol, 66.0% of C.sub.12 alcohols, 26.0% of C.sub.14 alcohol and
6.5% of C.sub.16 alcohol.
Another group of commercially available mixtures include the
"Neodol" products available from Shell Chemical Co. For example,
Neodol 23 is a mixture of C.sub.12 and C.sub.13 alcohols; Neodol 25
is a mixture of C.sub.12 and C.sub.15 alcohols, Neodol 45 is a
mixture of C.sub.14 and C.sub.15 alcohols. Neodol 91 is a mixture
of C.sub.9, C.sub.10 and C.sub.11 alcohols.
The dihydrocarbyl phosphites (D)(3) useful in the present invention
may be prepared by techniques well known in the art, and many
dihydrocarbyl phosphites are available commercially. In one method
of preparation, a lower molecular weight dialkylphosphite (e.g.,
dimethyl) is reacted with alcohols comprising a straight-chain
alcohol, a branched-chain alcohol or mixtures thereof. As noted
above, each of the two types of alcohols may themselves comprise
mixtures. Thus, the straight-chain alcohol may comprise a mixture
of straight-chain alcohols and the branched-chain alcohols may
comprise a mixture of branched-chain alcohols. The higher molecular
weight alcohols replace the methyl groups (analogous to classic
transesterification) with the formation of methanol which is
stripped from the reaction mixture.
In another embodiment, the branched chain hydrocarbyl group can be
introduced into a dialkylphosphite by reacting the low molecular
weight dialkylphosphite such as dimethylphosphite with a more
sterically hindered branched-chain alcohol such as neopentyl
alcohol (2,2-dimethyl-1-propanol). In this reaction, one of the
methyl groups is replaced by a neopentyl group, and, apparently
because of the size of the neopentyl group, the second methyl group
is not displaced by the neopentyl alcohol. Another neo alcohol
having utility in this invention is 2,2,4-trimethyl-1-pentanol.
The following examples illustrate the preparation of the phosphite
esters (B) which are useful in the compositions of the present
invention. Unless otherwise indicated in the following examples and
elsewhere in the specification and claims, all parts and
percentages are by weight, and all temperatures are in degrees
centigrade.
EXAMPLE (D)(3)-1
A mixture of 911.4 parts (7 moles) of 2-ethylhexanol, 1022 parts (7
moles) of Alfol 8-10, and 777.7 parts (7 moles) of
dimethylphosphite is prepared and heated to 125.degree. C. while
sparging with nitrogen and removing methanol as a distillate. After
about 6 hours, the mixture was heated to 145.degree. C. and
maintained at this temperature for an additional 6 hours whereupon
about 406 parts of distillate are recovered. The reaction mixture
is stripped to 150.degree. C. at 50 mm. Hg., and an additional 40
parts of distillate are recovered. The residue is filtered through
a filter aid and the filtrate is the desired mixed dialkyl hydrogen
phosphite containing 9.6% phosphorus (theory, 9.7%).
EXAMPLE (D)(3)-2
A mixture of 468.7 parts (3.6 moles) of 2-ethylhexanol, 1050.8
parts (7.20 moles) of Alfol 8-10, and 600 parts (5.4 moles) of
dimethylphosphite is prepared and heated to 135.degree. C. while
purging with nitrogen. The mixture is heated slowly to 145.degree.
C. and maintained at this temperature for about 6 hours whereupon a
total of 183.4 parts of distillate are recovered. The residue is
vacuum stripped to 145.degree. C. (10 mm. Hg.) and 146.3 parts of
additional distillate are recovered. The residue is filtered
through a filter aid, and the filtrate is the desired product
containing 9.3% phosphorus (theory, 9.45%).
EXAMPLE (D)(3)-3
A mixture of 518 parts (7 moles) of n-butanol, 911.4 parts (7
moles) of 2-ethylhexanol, and 777.7 parts (7 moles) of
dimethylphosphite is prepared and heated to 120.degree. C. while
blowing with nitrogen. After about 7 hours, 322.4 parts of
distillate are collected, and the material then is vacuum stripped
(50 mm. Hg. at 140.degree. C.) whereupon an additional 198.1 parts
of distillate are recovered. The residue is filtered through a
filter aid, and the filtrate is the desired product containing
12.9% phosphorus (theory, 12.3%).
EXAMPLE (D)(3)-4
A mixture of 193 parts (2.2 moles) of 2,2-dimethyl-1-propanol and
242 parts (2.2 moles) of dimethylphosphite is prepared and heated
to about 120.degree. C. while blowing with nitrogen. A distillate
is removed and collected, and the residue is vacuum stripped. The
residue is filtered nd the filtrate is the desired product
containing 14.2% phosphorus.
The compositions of the present invention comprising components (A)
and (B) or (A), (B) and (C) or (A), (B) and (D) or (A), (B), (C)
and (D) are useful in passenger car motor oils (PCMO), gear oils,
automatic transmission fluids (ATF), hydraulic fluids, chain bar
lubricants, way lubricants for machinery operations, diesel
lubricants and tractor fluids.
When the composition comprises components (A) and (B), the (A):(B)
weight ratio is generally from 75:25 to 99.9:0.1, preferably from
80:20 to 99.5:0.5 and most preferably from 85:15 to 99:1.
When the composition comprises components (A), (B) and (C) or (D),
the following states the ranges of these components in parts by
weight
______________________________________ Component Generally
Preferred Most Preferred ______________________________________ (A)
50-99 60-90 70-85 (B) 0.1-30 1-20 5-20 (C) or (D) 0.01-60 1-40 1-20
______________________________________
When the composition comprises components (A), (B), (C) and (D),
the following states the ranges of these components in parts by
weight
______________________________________ Component Generally
Preferred Most Preferred ______________________________________ (A)
40-99 60-90 70-85 (B) 0.1-30 1-20 5-20 (C) 1-60 5-50 10-40 (D)
0.01-25 0.1-20 0.5-15 ______________________________________
It is understood that other components besides (A), (B), (C) and
(D) may be present within the composition of this invention.
The components of this invention are blended together according to
the above ranges to effect solution. The following Table I outlines
examples so as to provide those of ordinary skill in the art with a
complete disclosure and description on how to make the composition
of this invention and is not intended to limit the scope of what
the inventors regard as their invention. All parts are by weight.
The parts of component (B) are adjusted to reflect an oil free
product; i.e., the RS80 content of Example (B)(1)-10 is 57%. The
2.135 parts utilized in Example 6 is oil free and component (A)
reflects that 57% RS80 content. Additional RS80 is utilized to give
97.85 parts RS80.
TABLE I
__________________________________________________________________________
100.degree. C. EX- VIS % INCREASE IN AMPLE (A) (B) (C) (D) (cST)
VIS
__________________________________________________________________________
1 100 PARTS 8.59 -- SUNYL 80 (BASELINE) 2 98.68 PARTS 1.308 PARTS
EXAMPLE 0.012 PARTS 14.46 68.3 SUNYL 80 (B)(1)-9 ALKYLATED PHENOL
WITHIN (B)(1)-9 3 90 PARTS 1 PART EXAMPLE (B)(1)- 10 PARTS 9.51
10.7 SUNYL 80 4 (Note) GLISSOFLUID A-9 4 90 PARTS 1 PART EXAMPLE
(B)(1)- 10 PARTS 10.45 29.3 SUNYL 80 8 (Note) GLISSOFLUID A-9 5 100
PARTS RS80 8.31 -- (BASELINE) 6 97.85 PARTS 2.135 PARTS EXAMPLE
0.015 PARTS 15.71 89.0 RS80 (B)(1)-10 ALKYLATED PHENOL WITHIN
(B)(1)-10 7 90 PARTS RS80 1 PART EXAMPLE (B)(1)- 10 PARTS 9.33 12.3
4 GLISSOFLUID A-9 8 90 PARTS RS80 1 PART EXAMPLE (B)(1)- 10 PARTS
10.24 23.2 8 GLISSOFLUID A-9
__________________________________________________________________________
Note: (B)(1)4 and (B)(1)8 were repeated using Sunyl 80 at an equal
replacement level.
* * * * *